Method of producing olefin sulphur dioxide resins



mgm-1942 'F. E.-FREY ETAL METHOD 0F PRonUcINGoLEFlN suLHun DIoxIDE russiNs Filed' Dec. 2s. 1959 INVENTOR .iiled January 31, 1936, which is now U.

Patented Aug. 25, 1942 METHOD oF PnonUCING moxrnn RESINS OLEFIN SULPHUR Frederick E. Frey and Robert D. Snow, Bartlesville, Okla Company,

., assignors to Phillips Petroleum a corporation of Delaware Application December 2s, 1939, serial No. 310,700

12 Claims.

'I'he'present invention relates to the production of resins, and in particular to the production of high molecular weight heteropolymeric resinous materials from sulphur dioxide and an unsaturated organic material, such as an oleiin hydrocarbon or a mixture of olen hydrocarbons, or other oleiinic compounds, Y

This invention is a continuation-in-part of our co-pending application, Serial No. 61,813,

S. Patent 2,184,295, and has among itsobjects the provision of an apparatus and method for continuously producing resins from unsaturated organic material and sulphur dioxide when thereactants are associated with substantialquantities of inert material such as paramn hydrocarbons of substantially the same boiling range as that of the unsaturated material.

In the art prior to our-co-pending application, Serial No. 61,813, of which the present application is a continuation-impart, the references to the production of oleiin-sulphur dioxideresins, or the like, describe the use of batch methods. The execution of such methods incurs the expensive construction and the high costs of operation for the numerous large reactors, specially designed to meet reaction conditions, inherent in discontinuous procedures of those methods. The application, Serial No. 61,813, discloses an apparatus and `method for continuously producing resins from unsaturated organic compounds and sulphur dioxide.

The objects of the present invention are to provide a process of a substantially continuous nature for reacting sulphur dioxide with unsaturated material which is associated with substantial quantities of inert material, which will generally have substantially the same boiling range b ut which may be deliberately added material of a different boiling range; to provide a. process wherein conditions are controlled in y regard to concentration, temperature, etc., so as to promote the formation of resinous material and to permit it to separate as a second phase, and especially as a i'luid or plastic phase that permits removal of this phase from the reactorin a substantially continuous manner or, if desirable, in substantial quantities at convenient intervals; and to provide means for the removal of the inert material from the reactor in sufficient quantities to prevent its accumulation to such an extent as to retard or stop the reaction while the reactants and catalysts are charged to the reactor in a substantially continuous manner. This invention provides means for deliberate addition, if desirable, of inert material such as paraffin hydrocarbons, in quantities suicient to suppress the solubility of the-resin in the reaction phase and to aid and promote the separation of the second phase.

Other' objects and advantages of this invention will become 'evident on consideration of the description given herein.

In connection with the present process, the iinsaturated lmaterial to be reacted with sulphur dioxide often is not ina substantially pure stater The material may be derived from the thermal or catalytic dehydrogenation of hydrocarbons, the products of cracking stills, or from other sources which produce material comprising large quantities of unsaturated compounds associatedwith parains of the same boiling range. The material thus obtained may be subjected to preliminary treatment, if desired, such as selective solvent extraction at low temperatures with liquid sulphur dioxide toconcentrate the rated material. In some cases, as when the charged unsaturated material contains large quantities of pentenes, hexenes and/or'higherl boiling olens, it may prove advantageous to make deliberate addition of inert material in requisite quantities to decrease the solubility of the resin in the reaction phase and to facilitate the separation of the resin phase, and to add such material during the reaction and to control its concentration so as to effect and aid` vseparation of the resinous product is a partof our invention. This may be especially true when unsaturated material other than unsaturated hydrocarbons are to be reacted with sulphur dioxide to form heteropolymeric resinous materials.

In practicing our present invention, means are provided for decreasing the concentration of inert material to within the limit of practicable operating conditions should such material tend to accumulate or attain too large proportions. If the ratio of inert material to the remaining quantity of charge stock is small, the rate of removal of this material with the resinous material, entrained 'or dissolved therein, will often unsatuthe desired concentration` vaporize If the charge stock contains large quantities and the material is of such or readily vaporizable,

of the inert material nature as to be gaseous,

under the conditions of the reaction, the concen-` tration of this inert material in the reaction mixture may be decreased by removing quantities of the vapors from the reactionzone. These separate these reactants from the inert material and to return these -reactants to the reaction chamber as will be more fully discussed; this can be done by condensing vapors so removed and subsequently cooling the mixture to the point of liquid separation into two layers or, in the case of appreciable solubility of the inert material in the solution, fractional distillation of this mixture may be eiected, or other vsuitable means of separation, to be more completely discussed, may be used. A

If the inert material is present in large quantities and is of such nature as to remain liquid under the reaction conditions, and dissolved in the reaction phase, the concentration may be decreased by removing a liquid sidestream from the phase which comprises the reacting materials, subjecting such withdrawn materials to appropriate treatment for separation of the inert material and the reactants, such as fractional distillation, with return of the reactants. At intermediate conditions of concentration, and depending upon the nature of the inert material, it may be found desirable to supply heat, sufficient to sufcient to increase the temperature unduly, or to labstract heat, sufficient to condense portions of the vaporous phase but not decrease the temperature, to elect changes in state and produce, as a result, conditions for more -practicable operation of means and methods providing decrease in concentration of the inert material, of vapors or of liquid.

The apparatus and method for practicing this invention will become evident in the description of the apparatus and method of operation given in connection with the attached drawing, which illustrates diagrammatically one form of apparatus for practicing the present invention.

The reaction materials, catalyst, sulphur dioxide, and unsaturated organic material, which may be associated with substantial quantities of inert material of substantially the same boiling range, are stored respectively in any suitable vessels such as those shown at I0, and I2. The desired quantities of these reaction materials are withdrawn through the pipes I3, I4 and I5, respectively by means of pumps I6, I1 and |8 into a common pipe I9, through which they pass to a mixer 20 of any convenient form. The mixer may beof a centrifugal, jet, orifice, baille or any other type desired. An inert material may be quantities of the liquid phase but not by removal within the reaction zone which enters the cooler added through pipe |00 controlled by valve lill,`

but should preferably have a small volume, so as to control the reaction in the reactor 22.

The mixture of the materials to be reacted ows, or is forced, from the mixer 20 through pipe 2| into the reactor zone, or reaction chamber 22, wherein the resm reaction of said mixture is effected.

fected inseveral different ways. The reactor zone or reaction chamber may be provided with internal cooling coils, or a jacket 23, as shown, into which a cooling medium enters at 24, and from which it leaves at 25 after circulating therethrough. The jacket 23 may be operated as a heating means to maintain the desired temperature should excessive vaporization occur, and to abstract heat in quantities suicient to decrease the temperature, when the heat of reaction is high.

Another means of controlling the temperature 22 comprises removing sucient sensible heat from the charge materials, namely catalyst, sulphur dioxide and unsaturated organic material which may be associated with inert material of substantially the same boiling range, by passing all or a part of them through a cooler 26 prior to mixing and introducing them into the reactor. The pipes |4 and I5 are shown passing through the cooler 26, serving as coils I4' and I5', and are cooled by a cooling medium by pipe 21, flows through the cooler and leaves by way of pipe 28. This method of cooling has the advantage of retarding or preventing reaction during mixing and charging of the reaction materials. The cooler 26 may be by-passed by suitable means, not shown, as will be readily appreciated.

The reaction zone 22 may be cooled by any other suitable means or methods, which may include the provision of a cooler and condenser 29 into which the vapors within the chamber 22 flow through pipe 30 and are cooled and condensed before flowing back throughv pipe 3| controlled by valve 3|', as reux to cool the reactor.

It is .frequently advantageous to agitate the charge undergoing reaction in chamber 22 and. for this purpose, an agitator 32 is shown mounted therein on a shaft 33 which may be supported and driven in any suitable manner.

As the resinous product forms in the bottom of the reactor, it is removed substantially continuously through pipes 34, 35 and 35a, controlled by valves 36. 3'I and 31a respectively. The pipes 35 and 35a leadto expansion chambers 38"and 38a as shown. The resinous product may pass through a heater 34 before entering the expansion chamber. It ispreferable to flow the resinous product into but one expansion chamber at a time, so by opening the valves 36 and 31 the product passes from the reaction chamber 22 through pipes 34 and 35 into the expansion chamber 38 where most of the volatile materials are removed by ash vaporization, and the resin is obtained in a very porous expanded form. The expansion chambers 38 and 38a are used alternately, one being lled with the resinous product fromV the reaction chamber 22 while vapors and resin` are being discharged and removed from the other. As many expansion chambers of the type shown at 38 and 38a as are needed or desired may be used, in accordance with the capacity of the reaction chamber 22. To facilitate the flash vaporization of the material entering the expansion chambers or zones, heating means of any suitable type may be provided, and heating coils 39 and 39a are shown as one means of heating the chambers. Each chamber 38 and 38a is provided with a suitable means for removing the resin, and in the structure shown it Vtakes the form of doors 40 and 40a.

Vapors are exhausted from the resin and the 38 and 38a through the pipes 4| and 4|a, which are controlled by the-valves 42 with the vacuum pump 44. The vapors' so withdrawn from the expansion chambers are cooled in the condenser 45 through which a cooling medium From the condenser xed gases are vented through the pipe 48 and bled out of the System, and therein the sulphur dioxide and any organic material are liquefied. If the concentration of inert'material is sufficiently low, so as not to retard the reaction in chamber 22, which would be true if the rate of removal of inert material entrained or dissolved in the resinous material is equal to orgreater than the rate of addition, the condensatemixture is passed by pipe 49 to a storage tank or accumulator 50, and thence into pipe through which it is forced by the pump ows, entering at 46 and leaving at 4l.-

v ever, be eected by the terial; the cooling in condenser -29 may, howuse of ordinary plant cooling water as the medium, in which case the cooled material is withdrawn through pipe |02 controlled by valves |05 and ||6 into a second Acooler and condenser ||5, which is supplied with a suitable cooling or refrigerating medium which extracts heat suilciently to cause further cooling and condensation, and separation of the liquid into two liquid layers. The material is withdrawn from condenser 29 through pipe |02 and valve |05 into separator |06 or, 'as partially cooled material, into cooler ||5 and thence into the l separator |06 as shown with proper control of 52 through the coil 52 of the cooler 26, for the purpose previously described, and then into pipe I9, mixer 20, and pipe 2| to the reaction chamber 22.

If the amount of inert material present in the condensate mixture from the condenser is such that its addition into reaction chamber 22 would increase the concentration of the inert material in the chamber beyond the limit of practicable operation, provisions must be made for the removalf'of quantities of the material. In order to accomplish this removal, a valve 53 is interposed in pipe |49 leading to the accumulator 50, and by closing it and opening the valve 5d in pipe 55 communicating with pipe 49 between the condenser 45 and valve 53, the condensate if fed to a fractionating column 56 from which an azeotropic mixture of hydrocarbon and sulphur dioxide is distilled overhead through the pipe 5l into the condenser l53, and through pipe 59 to the storage tank or accumulator 60. 'Ihe fractionating column may be provided with any suitable heating means such a's the steam coil shown at 56' and there may be interposed. in pipe 55 any type of suitable pump a. and a preheater 55h which is shown diagrammatically inthe drawing. Through the condenser 58 there is circulated any suitable cooling medium which enters through pipe 6| and leaves through pipe 62. From the fractionating column 56 a liquid comprising sulphur dioxide and/or unsaturated material is drawn oil at the bottom through pipe 63 as a kettle bottom product and introduced into the accumulator 50 from whence it iows through pipe 5| and ultimately reaches the reaction chamber 22.

The material leaving the top of the fractionating column is subjected to a reflux' condensation and, to eiTect this, vapors are led oi from the top of the column through pipe Se and after passing through the reiiux condenser illustrated diagrammatically at 65 they ow through pipe 56 into the top of the column 56. Any suitable means for cooling the reflux condenser may be employed, and in thedrawing it is illustrated as being cooled by a cooling medium which enters through pipe 68 and leaves by way of pipe 6l.

A The concentration of inert material in the chamber may becmaintained within the 'range of practicable operating conditions by decreasing the concentrationof the material in the gaseous phase in the reaction chamber. Vapors may pass from the top of the reaction chamber 22 through pipe 30 into the cooler and condenser 29. If desired, the cooling medium ln the condenser may be such that the vaporous material is condensed and sumclently cooled to cause separation bevalve ||4. From the separator, thel lighter layer, rich in inert vmaterial is removed from the system by pipe ||0 controlled by valve and the bottom liquid layer, rich in sulphur dioxide and unsaturated material, is passed to pipe 3| and returned to the reaction chamber |01 by means of valve |08, or it may be withdrawn from the system by means of valve |05.

Vapors may be withdrawn through pipe ||2 controlled by valve ||3.

An alternative method of treating the vapors will be found advantageous if a large concentration of an inert material such as butane or pentanes is present, since such material would be carried over at an appreciable rate with the sulphur dioxide fraction from separator iet and, in the presence of unsaturated material, is difcult to separate from liquid sulphur dioxide. The cooled material from the cooler and con- `denser 29, which need not be operated at a low subatmospheric temperature in this instance, is passedthrough valve |03 in pipe |04 andtransferred to the fractionating column 56 through valve |03a where the azeotropic mixture of hydrocarbon and sulphur dioxide is separated and passed into accumulator l, and a fraction comprising unsaturated material and sulphur dioxide.

drawn oi through pipe 63 into accumulator 53 as maintaining the concentration of inert material 1 Within the limits of practicable operating'con'ditions may be effective. This involves treatment of the liquid phase which comprises the reacting materials. When necessary, such quantities of the material are withdrawn, as a liquid side stream through pipe |20, as are required to decrease the concentration to the desired ratio, and the material is immediately treated with a substance i to kill, the catalyst or otherwise to inhibit the resin-forming reaction, this catalyst-inhibitor being introduced through pipe |23 and valve |2d, to prevent further resin-formation and the subsequent gumming-up or clogging of the apparatus. The mixture is passed into chamber |2| and subjected to ash vaporization whereby the volatile materials are removed and any resinous product that is present remains and may beremoved, as previously described in connection with the resin expansion chambers 38 and 38a, through pipe H8 and valve H9. The vapors pass from chamber |2| through pipe |25 and cooler |26 lnto'pipe |21, and through pump |28 and pipe |29 controlled by a valve |30 into pipe |04, and into the fractlonating column 55. When this means of removing inert material from the reaction 22 is employed, a suitable separation may often be effected by condensing and cooling the material so that two liquid phases are formed. In such a case the mixture 22 through pipe may be passed from of pump |36, which has a charge line |34 coni dioxide, and can cedure a large part of the unreacted,

trolled by a valve |35 leading from pipe |04, and a discharge line |31 controlledby valve |30 leading back to pipe |04, and this may be operated with the closing of valve |33 in pipe |04.

When the inert material is considerably higher boiling than sulphur dioxide, and fractional distillation in the column 56 is used for the separation, the inert material willpass from the bottom of the column 56 through pipe 63. In such a case, it will be substantially freed oi sulphur be discharged from the system through pipe controlled by a valve 1|, the valve 63' in pipe 63 being closed. With this modification, substantially all the sulphur dioxide will pass overhead through pipe 51 without being accompanied by inert material, and will be received in the accumulator 60 in a state suitable for recycling. This may readily be carried out by obvious means, not shown. Generally, however, in such a case it will be desirable to separate the sulphur dioxide and inert mate'- rial as two separate liquid phases, such as separator |06, as discussed. In this prounsaturated material is found in the liquid sulphur dioxide phase, and as such is readily returned to the reaction. In most cases will have a higher speciiic gravity than will any liquid inert material, and the separation will be as has been tionship is reversed, it will be readily appreciated that the various connections to separator |06 may be changed to meet the circumstances.

4It will now be seen that inert material may be removed from the reactor 22 when it has a high vapor pressure at the reaction temperature ,and also when it has a low vapor pressure, and when it is readily separated from liquid sulphur dioxide as an immiscible liquid as well as when distillation must be Iused for the separation.

The reaction of unsaturated material with sulphur dioxideto form heteropolymeric resinous materials of high molecular known, and may take place. in the presence of light, and/or in the dark when promoted by catalysts. In this regard, reference is made to U. S. Patents 2,045,592; 2,112,986; 2,128,932; 2,136,028 and 2,136,389 among others. When lower boiling unsaturated materials `are used, especially the lower boiling unsaturated hydrocarbons, they are often accompanied by inert saturated hydrocarbons of the same boiling range, even though a concentration step for such unsaturated hydrocarbons has been used.' Since in apparatus the liquid sulphur dioxideweight is' well often most expedient indicated. However, if this relai the reaction is selective to the unsaturated hyj drocarbons present, it in itself tends to concentrate the inert, saturated hydrocarbons, and thus has been described herein are necessary. In other cases where the lunsaturated materials are introduced to the process in' a substantiallypure state, especially with unsaturated materials having more than about six carbon atoms per molecule, the resinous prodducts are quite soluble in the reactant mixture.l and it is desirable adding an inert material to facilitate separation of the resin as it is produced. Since the reaction to alter this condition byI v temperatures generally are notvery high, it is 76 to add an inert material having a much lower boiling point than the unsaturated material, such as butane, pentane or hexane, and to do so is a part ot our invention. A fixed quantity of -such an inert material may be retained in the reactor, without drawing any out and without adding any, but when such inert material is added continuously, of low or high boiling point, it is conveniently removed as herein described.

We claim:

l. In a process in which an ole'iinic body reacts with approximately an .equimolar quantity of sulphur dioxide to form a high molecular weight heteropolymeric resinous product which separates from the reactants as a separate viscous liquid phase usually containing Vsome excess sulphur dioxide, the said oleflnic body being associated with substantial quantities ot inert material of substantially the same boiling range in which said resinous productis substantially insoluble, the steps which comprise charging to the reaction zone as reactants sulphur dioxide and a mixture containing said oleiinic body and said inert material, substantially continuously and in such proportion, in the presence of a catalyst for promoting the reaction, that a mass comprising said heteropolymeric resinous prod uct separates from t le reactants in said reaction zone as a separate viscous liquid phase, withdrawing a portion of the gaseous phase present in said zone, separating from said withdrawn material a fraction comprising said inert material and discharging it from the process, separating also a fraction comprising sulphur dioxide and returning said fraction to said reaction zone,

and separating from said reaction zone a viscous liquid containing said heteropolymeric resinous i rate viscous liquid 'phase containing some excess sulphur dioxide,

the said oleiinic material being associated with substantial quantities of relatively volatile inert organic material o! substantially the same boiling range in which said resinous product is substantially insoluble, the steps which comprise substantially continuously charging to` a reaction zone sulphur dioxide and said oleiinic material associated with said inert material, in the presence ora catalyst for promoting the reaction, maintaining a reaction temperature such that said reactants and inert material are present together in a iirst liquid phase, charging said materials in such proportions that a solution comprising high molecular weight heteropolymeric resinous material separates from said reactants as a second and viscous liquid phase,withdrawing a portion o! the gasei said volatile inert material and discharging said separating also from fraction from the process, said material a fraction comprising sulphur .dioxide and returning said fraction to said reaction zone, and substantially continuously withdrawing a material comprising said second liquid phase from said reactionl zone.

3. In a process for the production of a high molecular weight resinous product from sulphur dioxide and a relatively volatile rial which reacts with sulphur dioxide to form oleiinic mateterial along solubility oi'l the resin in the such a, product and which is associated 'with relatively volatile inert saturated organic material of substantially the same boiling range in which said resinous product is substantially insoluble, the steps which comprise feeding to a reaction zone, in the presence of a catalyst for promoting 'the reaction, sulphur dioxide in a liquid state and said olenic material associated with said inert material substantially continuously and in such proportions that a viscous solution of resinous product willseparate from the reactants, withdrawing a portion of the materialformi'ng a gaseous phase in said reaction zone, liquefying said material and subjecting it to a fractional distillation to separate overhead a vapor with sulphur dioxide and discharging said fraction from the system, separatingas a .kettle product a fraction comprising said olenic material and returning said fraction to said jreaction zone, and substantially continuously withdrawing said viscous solution of resinous product from said reaction zone.

4. In a process for the production of a high molecular weight heteropolymeric resin from sulphur dioxide and a relatively volatile olenic material which reacts with sulphur dioxide to form such a resin and which is associated with a relatively volatile inert saturated organic material of substantially the same boiling range in which said resin is relatively insoluble, the steps which comprise charging to a. reaction chamber -in a liquid state sulphur .dioxide and said olefinic material associated withv said inert material substantially continuously and in such proportions, in the presence of -a catalyst for promoting the reaction, that a Viscous solution of the resin will-separate from the reactants, withdrawing a portion of the material forming a gaseous phase in said reaction chamber, liquefying said material and cooling it to a low temperature to cause said material to separate into two liquid phases consisting of an upper liquid phase comprising said inert material and a lower liquid phase comprising sulphur dioxide and volatile olenic material, discharging said upper liquid phase from the process, passing said lower liquid phase to said reaction chamber, and substantially continuously withdrawing said solution of resin from said reaction chamber.

5. vIn a process for the production of a high molecular weight heteropolymeric resinous product from sulphur dioxide and an oleiinic material which reacts with sulphur dioxide to form such a product, the steps which comprise subfraction comprising said inert ma'- Y stantially continuously charging to a reaction i chamber sulphur dioxide and said olenic material in such proportions, in the presence of a catalyst for promoting the reaction, that the resin-formingreaction takes place, introducing such quantities of volatile inert material in which said resinous product is relatively insoluble into the reaction zone as will suppress the reaction phase and a separate viscous resinous product,

facilitate the separation of liquid phasecomprising the withdrawing a portion of the gaseous phase present in'said zone, separating from the withdrawn `material a fraction comprising said inert material and discharging said fraction from the process, separating also from said material a fraction comprising sulphur dioxide and returning said fraction to said reaction zone, and substantially continuously withdrawing from the zone a viscous liquid containing said heterop'olymeric resinous product.

6. `In a process for the production of a high molecular weight heteropolymeric resinous product from sulphur dioxide and an olelnic material which reactsv with sulphur dioxide to form such a product, the steps which comprise substantially continuously charging to a reaction chamber sulphur dioxide and said oleilnic mamaterial a fraction comprising said inert mate rial and discharging said fraction from the ess, separating also from said material a procfraction comprising sulphur dioxide and returning said fraction to said reaction chamber, and substantially continuously withdrawing from the chamber a viscous liquid containing said heteropolymeric resinous product.

7.' In a process for the production of a high molecular weight heteropolymeric resin lfrom sulphur dioxide and an olenic material which reacts with sulphur dioxide to form such a resin and which is associated with inert material of substantially the'same boiling range in which said resin is relatively insoluble, the steps which comprise charging to a reaction chamber in a liquid state sulphur dioxide and said olefinic material associated with said inert material substantially continuously and .in such proportions, together with a catalyst for promoting the reaction, lthat a viscous solution of the resin will separate from the reactants, withdrawing a fraction as a liquid side stream from the phase comprising lthe reacting materials, introducing a catalyst-inhibitor to said withdrawn fraction and subjecting the mixture to ash vaporization, withdrawing the Vaporous products from said vaporization and separating said products by fractional distillation into a vapor fraction com.- prising said inert material' along with sulphur dioxide, discharging said fraction fromthe system, separating also as a kettle product a iraction comprising olelnic material and sulphur dioxide, returning said fraction to said reaction zone, and substantiallycontinuously withdrawing as a separate liquid a portion of said viscous solution containing said heteropolymeric resinous product from said reaction chamber.

8. In a process for the production of a heteropolymeric resinous product of high molecular weight from sulphur'dioxide and an olelinic organic material which reacts with sulphur dioxide to form such a resinous material, the steps which comprise substantially continuously charging the said oleiinic material and sulphur dioxide, said sulphur dioxide being present in excess of that amount required as a reactant, to a reaction chamber under suilicient pressure to maintain at least a major portion of said reactants in a liquid phase in said reaction chamber, promoting a reaction lbetween said olenic material and said sulphur dioxide to form a hetferopolymeric resinous material, maintaining in said reaction chamber butane in a concentration suiiicient to aid the separation of said heterotion suilicient to ald oxide, said sulphur dioxide being material and said sulphur polymeric resinous material as a separate viscous liquid phase containing sulphur dioxide and in a concentration insufficient to inhibit said reaction excessively, andwithdrawing from said reaction chamber said heteropolymeric resinous material.

9. In a process for the production of a heteropolymeric resinous product of high molecular weight from sulphur dioxide and an olenic organic material which reacts with sulphur dioxide to form such a resinous material, the steps which comprise substantially continuously charging the said oleiinic material and sulphur dioxide, said sulphur dioxide being present in excess of that amount required as a reactant, to a reaction chamber under suiilcient pressure to maintain at least a major portion of said reactants in a liquid phase in said reaction chamber, promoting a reaction between said olefinic material and said sulphur dioxide to form a heteropolymeric resinous material, maintaining in said reaction chamber pentane in a concentrathe separation -of said heteropolymeric resinous material as a separate viscous liquid phase containing sulphur dioxide and in 'a' concentration insuflicient lto inhibit said reaction excessively, and withdrawing from said reaction chamber said heteropolymeric resinous material.

10. In a process for the production of a heteropolymeric resinous product of high molecular weight from sulphur dioxide and -an olenic organic material whichreacts with sulphur dioxide to form such a resinous material, the steps which comprise substantially continuously charging the said oleflnic material and sulphur dipresent in excess of that amount required as a reactant, to a reaction chamber under suilicient pressure to maintain at least a major portion of said reactants in a liquid phase in said reaction chamber, promoting a reaction between said olefinic eropolymeric resinous material, `maintaining in said reaction chamber hexane in a concentration suillcient to aid the separation of said heteropolymeric resinous material as a separate viscous liquid phase containing sulphur dioxide and in a concentration insulcient to inhibit said reaction excessively, and withdrawing from said reaction chamber said heteropolymeric resinous material. c

11. In a process in which an oleflnic material reacts with approximately an equimolar quantity dioxide to form a hetboiling mixture of ,50 cous liquid from said of sulphur dioxide to form a heteropolymeric resinous product soluble in liquid sulphur dioxide, the improvement which comprises substantially continuously yfeeding to a reaction chamber as liquids said oleilnic material, sulphur dioxide in an amount in excess 'of that molecularly equivalent to said unsaturated material, and suilicient inert saturated hydrocarbon material in which the resinous product is substantially insoluble to suppress the solubility of the resin in the liquid reaction phase and facilitate the separation of a separate viscous liquid phase comprising sulphur dioxide and the resinous product, promoting a reaction in said reaction chamber between said unsaturated material and said sulphur dioxide to form a heteropolymeric resinous product, removing from said reaction chamber a mixture comprising inert material and unreacted sulphur dioxide and substantially free of said resinous product, separating sulphur dioxide from said inert material and returning said sulphur dioxide to said reaction chamber, separately withdrawing a portion of said viscous liquid phase from said reaction chamber containing sulphur dioxide and said heteropolymeric resinous product, and recovering therefrom a heteropolymeric resinous product so produced.

12. A continuous process for the production of heteropolymeric resinous products of the reaction of sulphur dioxide with an unsaturated organic material comprising normal .butenes associated with normal butane, which comprises substantially continuously charging to a reaction chamber'as liquids such an unsaturated material and sulphur dioxide in an amount in excess of that molecularly equivalent to said unsaturated material, promotingY a reaction between said unsaturated material and sulphur dioxide to form a heteropolymeric resinous product which separates from the reaction mixture as a viscous liquid, withdrawing a portion of the. gaseous phase present in said reaction chamber, subjecting said material toa fractional distillation to separate as an overhead product a minimumsulphur dioxide and butane and as a kettle product a fraction comprising unsaturated organic material, returning said unsaturatedmaterial to said reaction chamber,

substantially continuously withdrawing said vistherefrom a resinous product so produced.

FREDERICK E. FREY. ROBERT D. sNow.

chamber and recovering l 

